Substituted 1, 2, 4-thiadiazolidin-3, 5-diones and process therefor



United States Patent Ufihce 3,374,240 SUBSTITUTED1,2,4-THIADIAZOLIDlN-3,S-DIONES AND PROCESS THEREFOR Gerhard F. Ottmann,Hamden, and Haywood Hooks, Jr.,

West Haven, Conn, assignors to Olin Mathieson Chemical Corporation, NewHaven, Conn., a corporation of Virginia No Drawing. Continuation-impartof applications Ser. No. 411,638, Nov. 16, 1964, and Ser. No. 427,088,Jan. 21, 1965. This application June 29, 1965, Ser. No. 468,121

4 Claims. (Cl. 260-3067) This application is a continuation-in-part ofSer. No. 411,638, filed Nov. 16, 1964, now Patent No. 3,301,894, and ofSer. No. 427,088, filed Jan. 21, 1965 now abancloned.

This invention relates to a series of substituted 1,2,4-thiadiazolidin-3,S-diones, and more particularly it relates to cyclicderivatives having the following general formula:

(I) wherein both R and R are either alkyl, cycloalkyl, aryl, substitutedaryl or benzyl.

It has recently been established that S-chloro isothiocarbamyl chloridesreact with a wide variety of isocyanates to provideS-[N-(chlorocarbonyl) amino] isothiocarbamyl chlorides, and thepreparation of these latter de rivatives is thoroughly described anddisclosed in the aforementioned copencling application S.N. 411,638.These reactions proceed in accordance with the following equationwherein R and R are as represented in the preceding discussion.

It has now been found that the heretofore unknown cyclic derivatives (1)are provided in high yield and purity by the reaction of the S- [N'-(chlorocarbonyl)- amino] isothiocarbamyl chlorides with water. Anefiicient process for the preparation of the compounds (I) has beenprovided and is disclosed herein. The substituted1,2,4-thiadiazolidin-3,5-diones (I) are prepared in accordance with thefollowing equation.

Although the cyclic derivatives (I), wherein R and R are as previouslyrepresented, are readily prepared in accordance with the disclosureherein, preferred embodimerits of this invention include those compoundsof the general Formula I wherein both R and R are independently selectedfrom the class consisting of alkyl having l-l8 carbon atoms, cycloalkylhaving 5-7 carbon atoms, aryl having 6-10 carbon atoms, halogenatedphenyl, nitrated phenyl, benzyl and phenyl having a lower alkoxy (1-3carbon atoms) substituent. The preparation of the particular S-[N'(chlorocarbonyl) amino] isothiocarbamyl chlorides which can be convertedto these preferred embodiments is described in detail in our copendingapplication Ser. No. 411,638.

The cyclic derivatives (I) are obtained by treating theS-[N-(chlorocarbonyl) amino] isothiocarbamyl chlorides with water andisolating the desired products. Although the process can be readilycarried out at a tempera- 3,374,240 Patented Mar. 19, T568 ture range ofabout 0 C. to C., generally a preferred reaction temperature range ofabout 2040 C. should be employed. Isolation of the cyclic compounds (I)is accomplished by conventional procedures including, for example,extraction, distillation and filtration techniques. The substituted1,2,4-thiadioazolidin-3,S-diones of this invention are valuableagricultural chemicals especially as foliar and soil fungicides. Thecyclic derivatives (1) have also been found to be useful nematocides,and several of the novel cyclic compounds are quite active herbicides.Generally in these applications, they are utilized in the form ofmixtures with carriers and diluents known to those skilled in this art.For instance, they can be admixed with solid carriers to form activepowders and dusts. They are also readily formulated in the form ofemulsion concentrates suitable for dilution with water when admixed withappropriate organic solvents and emulsifying agents. The followingexamples will serve to illustrate the preparation of several of thesubstituted 1,2,4-thiadiazolidin-3,5-diones (I) in accordance with thisinvention.

Example 1 An amount of 40.0 g. ofN-butyl-S-[N-(chlorocarbonyl)-butylamino] isothiocarbamyl chloride wasadded increment-wise and with vigorous stirring over a period of 15minutes to 300 ml. of water which was heated to 70 C. When the additionwas completed the reaction mixture was agitated for 15 more minutes atthe said temperature and then was cooled to room temperature. Theorganic layer was separated by extraction with ether. The etherealsolution was dried with potassium carbonate, filtered, and the solventevaporated. The residue was distilled yielding 25.0 g. (77.5% of thetheory) of 2,4-dibutyl-1,2,4-thiadiazolidin 3,5 dione (B.P. 111 C./ 0.6mm., 21 1.4960) in the form of a colorless liquid.

Analysis.Calcd. for C H N O S: C, 52.14; H, 7.94; N, 12.30; S, 14.23.Found: C, 52.14; H, 7.88; N, 12.18; S, 13.90.

ExampleZ An amount of 30.0 g. of N-phenylS-[N'-(chlorocarbonyl)-ethylamino] isothiocarbamyl chloride was addedincrement-wise with agitation over a period of 30 minutes to 300 ml. ofwater at 25 C. The very exothermic reaction raised the temperature ofthe reaction mixture to 55 C. After complete addition, the mixture wasboiled for a short period and then cooled to 0 C. A precipitate wasseparated by filtration, and purified by recrystallization from n-hexaneyielding 22.0 g. of 2-ethyl-4-phenyl- 1,2,4-thiadiazolidin-3,S-dione,M.P. 94 C., in the form of white needles.

Analysis.-Calcd. for C H N O S: C, 54.05; H, 4.53; N, 12.61; S, 14.40.Found: C, 54.06; H, 4.49; N, 12.39; S, 14.75.

Example 3 An amount of 39.0 g. of N-phenylS-[N-(chlorocarbonyl)-p-tolylamino] isothiocarbamyl chloride was treatedwith water as described in Example 2. A solid precipitate was removed byfiltration, dried in vacuo, and recrystallized from 800 ml. ofn-heptane. Yield: 25.0 g. of2-(ptolyl)-4-phenyl-1,2,4-thiadiazolidin-3,5-dione, M.P. 134- 135 C., inthe form of white, silky needles.

Analysis.Calcd. for C H N O S: C, 63.37; H, 4.23; N, 9.86; S, 11.25.Found: C, 63.89; H, 4.42; N, 10.04; S, 11.36.

Examples 4-10 Using procedures similar to those employed in Examplesl-3, many other substituted 1,2,4-thiadiazolidin-3,5- diones included inthe general Formula I have been prepared in high yield and purity.Several of these prepared derivatives are tabulated in the followingtable.

lidin-3,5-dines which comprises reacting S-[N'-(chlorooompmnd Prepared5" 3:19:51 carbony1)-arnino] isothiocarbamyl chlorides with water 20cty1 4 0thyl 1,zHhiadiazolidmsdione (I) 76 and isolating thesubstituted 1,2,4 thiadia7olid1n 3, Zids propyI-I-phenyI-I,2,4-thiadiazolidin-3,5- 112113 95 dlonesh d one 2-b11ty1-4-phenyl-1,2,4thiadiazo1id -3,5-dione. 81-82 90 5 .5? gp i i2-0etyli14-phfiy2l-41ffi i-giiadiaoligin-g,5-di0ne. 1%; 11 2 ,S- ig i alg p ii reat1ngh b 1 2mm yw i3 111101 a c orocar ony amino] isot iocaramy 185 81 838918 ?!ffiifi iff'jiffiii fitffiiifi. 170 st chlorides ofthe formula 2-(p-methoxypheny1)-4-phenyl-1,2,4-thiadiazo- Ilidiu-3,5-dione 157-152 85 13.1. 134 O./0.6 mm. m

The ring structure of the compounds disclosed herein C1 C! has beenconfirmed by several procedures. The products, wherein both R and R areindependently selected formed y the reaction of the y from the classconsisting of alkyl having 1-18 carbon amino] isothiocarbarnyl chlorideswith water, are reduced 1 atoms, l lk l h i 5-7 carbon atoms, aryl h byreaction with lithiunralurninum hydnde to provide in in 640 carbonatoms, halogenated phenyl, nitrated every instance the correspondingN,N'-disubstituted ureas phenyl, benzyl and phenyl having a lower alkoxyin good yield. Moreover mass spectroscopy analysis has b tit t; ithconfirmed that the substituted 1,2,4-thiadiazolidin-3,5- (13) water at atemperature range of about 0 C, to diones have been Obtained- 100 C.,and separating said -3,5-di0nes from the What is claimed is: reactionmixture.

1. A compound of the formula References Cited 0 i UNITED STATES PATENTS\N 2,863,803 12/1958 Benghiat et al. 167-33 r OTHER REFERENCES Bradsheret al.: J. Am. Chem. Soc., vol. 80, pages 414- wherein R is aryl of 6-10carbon atoms and R is phenyl 417 (1958). having a lower alkoxysubstitucnt. Elderfield: Heterocyclic Compounds, vol. 7 (New York,

2. 2-p-methoxypheny1)-4-phenyl-1,2,4 thiadiazolidin- 1961), pages 563,567, and 575. 3,5-dione.

3. A process for preparing substituted 1,2,4-thiadiazo- ALTON D.ROLLINS, Primary Examiner.

1. A COMPOUND OF THE FORMULA
 3. A PROCESS FOR PREPARING SUBSTITUTED1,2,4-THIADIAZOLIDIN-3,5-DIONES WHICH COMPRISES REACTINGS-(N''-CHLOROCARBONYL)-AMINO) ISOTHIOCARBAMYL CHLORIDES WITH WATER ANDISOLATING THE SUBSTITUTED 1,2,4-THIADIAZOLIDIN-3,5DIONES.